Method of growing oxide films

ABSTRACT

Abstract of Disclosure 
     Process for producing silicon oxide containing thin films on a growth substrate by the ALCVD method.  In the process, a vaporisable silicon compound is bonded to the growth substrate, and the bonded silicon compound is converted to silicon dioxide.  The invention comprises using a silicon compound which contains at least one organic ligand and the bonded silicon compound is converted to silicon dioxide by contacting it with a vaporised, reactive oxygen source, in particular with ozone.  The present invention provides a controlled process for growing controlling thin films containing SiO 2 , with sufficiently short reaction times.

Cross Reference to Related Applications

[0001] The present application is a U.S. national phase applicationunder 35 U.S.C. § 371, based on PCT/FI00/01072, filed December 4, 2000,and claims priority under 35 U.S.C. § 119 to Finnish Patent ApplicationNumber FI 19992616, filed December 3, 1999.

Background of Invention Field of the Invention

[0002] The present invention relates to a method according to thepreamble of Claim 1 of producing oxide films.

[0003] According to such a method a thin film containing silicon dioxideis produced on a growth substrate by an ALD method by bonding avaporisable silicon compound onto the growth substrate and convertingthe bonded silicon compound to silicon dioxide.

[0004] The invention also relates to a method according to the preambleof Claim 20 of producing multicomponent oxides (i.e. mixed oxides ortertiary oxides).

Description of the Related Art

[0005] The continual decrease in the size of microelectronics componentsis leading into a situation in which SiO₂ can no longer be used as thegate dielectric (gate oxide) of MOSFET (metal-oxide-semiconductorfield-effect transistor) since for achieving required capacitances theSiO₂ layer should be made so thin that the tunneling current increasesdisadvantageously high from the functional point of view of thecomponent. To avoid the problem SiO₂ has to be replaced by a dielectricmaterial with higher dielectric constant. In that case a thicker layerof the dielectric material than SiO₂ can exist. Similarly thecapacitance of DRAM (Dynamic Random Access Memory) capacitors mustremain nearly constant meanwhile their decrease expeditiously in size,thus the previously used SiO₂ and Si₃N₄ have to be replaced withmaterials having higher dielectric constants than these.

[0006] Materials having sufficiently high dielectric constants areabundant, but the problem is that the considered dielectric should bestable on the silicon surface, should most preferably be amorphous andshould endure nearly unchanged under high post-treatment temperatures.Especially in the gate dielectric application a state where electricallyactive defects are rare should be provided at the interface of siliconand the high permittivity metal oxide. In the memory application thestructure of the capacitor dielectric must be very stable due to theapplied high activation temperatures. Due to the above mentioned factsit is preferable to admix SiO₂ to the metal oxide with a higherdielectric constant.

[0007] In its various forms Chemical Vapor Deposition (CVD) is the mostfrequently used method of producing silicon dioxide (see patentpublications JP 9306906, US 4 845 054, US 4 981 724, US 5 462 899, JP20868486, JP 6158329, JP 80061810, US 4 872 947, JP 7026383, US 5 855957 and US 5 849 644). Mainly tetraethoxy silane (TEOS) has been used asthe silicon source material, and oxygen, water, hydrogen peroxide orozone have been used as the oxygen source material in the patentpublications. In the conventional CVD the oxygen source material isalways brought simultaneously with the silicon source material to thegrowth substrate.

[0008] The conventional CVD method is related to the difficulty ofcontrolling the process, and neither a sufficiently good coverage withthe thin layers nor a good conformality is always achieved by CVD.

[0009] The invention is based to the idea that thin films containingsilicon dioxide are produced by the Atomic Layer Chemical VaporDeposition (ALCVD) process, which is generally known also as AtomicLayer Epitaxy (ALE) or Atomic Layer Deposition (ALD).

[0010] ALD is a current method of growing thin films (US patentpublication 4 085 430). According to the method a thin film is grown bymeans of saturable surface reactions, which are well separated from eachother. The saturation is provided by means of chemisorption. In otherwords, the reaction temperature is selected as that the gaseous sourcematerial is stable at the growth temperature and additionally, it doesnot condense or decompose on the surface but is capable to reactselectively with the reactive sites of the surface, e.g. with the OHgroups or oxygen bridges (M-O-M) present on the oxide surface. OH groupsfunctioning as reactive sites a so-called ligand exchange reaction takesplace in which a covalent bond is formed between the surface and thesource material (chemisorption). When the oxygen bridges are concerned adissociating reaction takes place in which reaction a covalent bond isalso formed (chemisorption). The bond formed by chemisorption is verystrong and the surface structure formed on the surface is stable whichenables the saturation of the surface by one molecular layer. The ligandexchange reactions are carried out by leading the gaseous or vaporisedsource materials alternately into the reactor and by purging the reactorwith an inert gas between the pulses of the source materials (T.Suntola, Thin Solid Films 215 (1992) 84; Niinisto et al. MaterialsScience and Engineering B 41 (1996) 23). Also even and uniform films canbe grown by ALD even on large surface areas. Accordingly films can begrown on both even and heterogeneous surface as well as on a groovedsurface. Controlling the thickness and the composition of the film bymeans of the number of reaction cycles is precise and simple.

[0011] Silicon dioxide has also been gown by the ALD process. CompoundsSi(NCO)₄ and N(C₂H₅)3 (K. YamagucHi et al., Appl. Surf. Sci.(1998)130-132) have been used as source materials. Producing silicondioxide by Molecular Layer ALE and UHV-ALE processes using SiCl₄ and H2Oas source materials is also known in the literature (Surface Review andLetters, Vol. 6, Nos 3 & 4 (1999) 435 - 448).

[0012] The disadvantages of these known solutions are long reactiontimes, for what reason the proposed processes cannot be realized on anindustrial scale.

[0013] The objective of the present invention is to eliminate thedisadvantages related to the prior art and to provide a novel method,which enables a controlled growth of SiO₂ containing thin films withsufficiently short reaction times.

Summary of Invention

[0014] The invention is based to the discovery that the above mentionedobjectives can be achieved by using a silicon compound containing anorganic ligand as the silicon source and a reactive oxygen source, suchas ozone, as the oxygen source material. Multicomponent oxides in whichthe amount of silicon dioxide can be varied in a controlled way caneasily be prepared by the proposed solution.

[0015] Furthermore, in the connection of the invention it hassurprisingly been found that while growing multicomponent oxides, i.e."tertiary oxides", by the ALD method from the corresponding sourcematerials of silicon and some other semimetal or metal and by usingsuitable oxygen sources the growth rate of the multicomponent oxide ishigher than that of either individual oxide. According to the inventionthe multicomponent oxides are therefore prepared by binding from the gasphase a suitable, vaporised silicon compound onto the growth substrate,converting the bonded silicon compound to silicon dioxide, bonding fromthe gas phase a vaporised metal compound or a vaporised compound ofanother semimetal onto the growth substrate and converting the bondedmetal compound or the compound of another semimetal to a correspondingoxide whereby the silicon compound and the compound of another semimetaland/or metal are bonded onto the growth substrate in a desired order.

[0016] More precisely, the method for preparing oxide films according tothe first embodiment of the invention is characterized by what is statedin the characterizing part of claim 1.

[0017] The method of preparing multicomponent oxide films according tothe invention is in turn characterized by what is stated in thecharacterizing part of claim 20.

[0018] Remarkable advantages are achieved with the aid of the invention.Thus, the ALD process provides a possibility far growing a multistagedinterlayer containing both silicon dioxide and metal oxide prior togrowing the actual metal oxide, which has a high dielectricity. Thestability of the capacitor dielectric can be increased by mixingamorphous silicon dioxide into the dielectric. The preparing ofmulticomponent oxides and the advantages achieved thereof are describedin more detail below.

[0019] It is to be noted that with the aid of the invention also puresilicon dioxide films can however be prepared. Such a silicon dioxidematerial can be used further in so-called STI (shallow trench isolation)structure. The function of STI is to isolate the transistors from eachother in both the circuit and memory structures. At present in thelateral direction wide so-called LOCOS isolation is in use, whichisolation is not suitable in the future circuits because of itsbulkiness. In STI technology a horizontal narrow deep trench filled withdielectric = silicon dioxide, is etched between the circuits. Since thedepth of the trench is greater than the width STI requires a methodwhich is capable of filling the etched isolation trench conformally. Bythe conventional CVD method STI trenches can be filled but often thetrench has to be widened in the upper part in order to avoid voidformation in the middle of the STI isolation. Enlargement of the trenchleads to increase of the STI area, i.e., the area of the isolation areaincreases. ALD is an especially suitable process for producing STIbecause ALD is characterized by the ability to grow silicon dioxide ofuniform quality and without void formation on uneven growth substrates,especially also onto narrow trenches. Using ALD enables thus a narrowerisolation area between the circuits whereby the packing density of thecircuits can be increased.

[0020] In the components needed in magnetic recording silicon dioxidecan be used as the isolation layer in both the writing/reading head andin the encapsulation of the writing/reading head. In order to avoid thedestruction of the magnetic properties of the layers, that are alreadybuilt, the processing temperature must be low in all steps. In general,physical (sputtering) methods are used in the field, the problem of saidmethods being the unevenness of produced film. ALD bas the capability toproduce both physically and electrically homogenous thin film. It isespecially preferable to use a low temperature ALD silicon dioxideprocess that provides a uniformly covering and electrically homogenousSiO₂ thin film. In this way the reproducibility and reliability of thisprocess step can be increased.

[0021] In the field emission displays (FED) film deposition methodsproducing uniform thin film on a large surface are needed. Due to thelow growth temperature and the uniformity of the silicon dioxide filmproduced the ALD silicon dioxide process is very suitable for preparingthe dielectric layer for the field emission displays.

[0022] By using especially reactive oxygen sources such as ozone,peroxide and oxygen radicals for converting the bonded silicon compoundthe forming temperature of silicon dioxide can be significantlydecreased. According to the invention it can be operated especially at atemperature lower than 450 °C, most preferably at 400 °C at the most. Inthat case the whole growing cycle can also be accomplished at the sametemperature, which has a great significance for industrial processing.Additionally, by using these reactive oxygen sources a very wide groupof organic silicon compounds, which are not possible to be converted bye.g. water, become available.

[0023] In the following the invention is viewed more closely with theaid of a detailed description.

Detailed Description

[0024] In the solution according to the invention silicon dioxide thinfilms and films mixed with silicon dioxide are grown in the ALD reactorpreferably at the temperature of 150 - 450 °C. Even flat (such as glassor wafer) or grooved flat materials can be used as a substrate. On thesurface of the substrate can also exist a so-called HSG (hemisphericalgrain) structure on which the film is grown. Additionally, a powderymaterial, which has a large surface area, can be used as a substrate.The term "growth substrate" designates in this invention the surface onwhich the thin film is grown. The surface can consist of theabove-mentioned substrate or of a thin film grown onto the substrate orof another structure.

[0025] According to the ALD process the silicon source material isvaporised and led onto the substrate on which it reacts and forms via aligand exchange reaction or dissociation reaction one chemisorbedmolecular layer on the surface. After the reaction the reaction space ispurged carefully with an inert gas to remove the unreacted sourcematerial and reaction products from the reaction space. In theconnection of this invention vaporisable compounds of silicon, whichcontain at least one organic ligand, are used as the silicon sourcematerial. "Organic ligand" designates a hydrogen carbyl group, which isderived from an organic compound. Such a ligand has thus itself a C-Cbond (e.g. an ethyl group) or it is bonded via carbon to the siliconatom or it has a C-H bond(s). According to a preferred embodimentsilane, siloxane or silazane are used as vaporisable silicon compounds.These are commercially available compounds.

[0026] Especially preferably a silicon compound, which has a boilingpoint of 400 °C at the most at a pressure of 10 mbar is selected. Thusthe ALD process can be carried out in the above-mentioned preferredtemperature range of 150 - 400 °C.

[0027] The following can be mentioned as examples of the preferredsilane, siloxane and silazane compounds: $\begin{matrix}\begin{matrix}{{Silanes}\quad {of}\quad {the}\quad {formula}} \\{{Si}_{m}L_{{2m} + 2}} \\{{{wherein}\quad m\quad {is}\quad {an}\quad {integer}\quad 1\text{-}3},}\end{matrix} & (I) \\\begin{matrix}{{Siloxanes}\quad {of}\quad {the}\quad {formula}} \\{{Si}_{y}O_{y - 1}L_{{2y} + 2}} \\{{{wherein}\quad y\quad {is}\quad {an}\quad {integer}\quad 2\text{-}4},{and}}\end{matrix} & ({II}) \\\begin{matrix}{{Silazanes}\quad {of}\quad {the}\quad {formula}} \\{{Si}_{y}{NH}_{y - 1}L_{{2y} + 2}} \\{{wherein}\quad y\quad {is}\quad {an}\quad {integer}\quad 2\text{-}4.}\end{matrix} & ({III})\end{matrix}$

[0028] In formulae (I) - (III) each L can independently be F, Cl, Br, I,alkyl, aryl, alkoxy, vinyl (-CH = CH₂), cyano (-CN), amino, silyl(H₃Si-), alkylsilyl, alkoxysilyl, silylene or alkylsiloxane wherebyalkyl and alkoxy groups can be linear or branched and contain at leastone substituent. Typically alkyl and alkoxy groups contain 1 -10 carbonatoms, most preferably 1 - 6 carbon atoms.

[0029] As examples of especially preferred silicon compoundsamino-substituted silanes and silazanes, such as 3-aminoalkyltrialkoxysilanes, for example 3-aminopropyltriethoxy silaneNH₂-CH₂CH₂CH₂-Si(O-CH₂CH₃)₃ (AMTES) and 3-aminopropyltrimethoxy silane(NH₂-CH₂CH₂CH₂-Si(O-CH₃)₃ (AMTMS) and hexa-alkyldisilazane(CH₃)₃Si-NH-Si(CH₃)₃ (HMDS) can be mentioned.

[0030] The silicon compound can also be formed during the ALD process inthe connection of gas-phase reactions so that while the silicon compoundis bonding, a new gas-phase silicon compound is formed which in turn isable to bond to the hydroxyl and, optionally oxide groups of the growthsubstrate. In this invention this phenomenon is called "in situ"formation of silicon compound. Such an in situ formed silicon compoundcomprises typically a silane compound, e.g. a silane compound which hasa formula SiL₁L₂L₃L₄, wherein L₁ represents an amino group and L₂ - L₄represent alkyl or alkoxy group. This silane compound is formed e.g.when the growth substrate is contacted with hexa-alkyldisilazane at350 - 450 °C at the pressure of 0,1 - 50 mbar.

[0031] After bonding the silicon compound a suitable reactive oxygensource is introduced into the reaction space, said oxygen sourceproviding the conversion of the silicon compound to silicon dioxide onthe growth surface. In the following the invention is described moreclosely having ozone as an example. It must however be noted thatinstead of ozone also other oxygen source materials, listed below moreprecisely, can be used in many cases. Using ozone numerous advantagesare however to be achieved as far as the spectrum of the siliconcompounds used and the processing temperature are concerned.

[0032] Ozone, which is introduced into the reaction space, reacts withthe ligands of the chemisorbed silicon source material forming OH groupsand oxygen bridges on the surface. In other words ozone combusts theorganic ligands and water formed in the combustion reaction formsfurther OH groups. After the reaction the reaction space is purged verycarefully again with an inert gas to remove the unreacted ozone and thereaction products. These four steps together form one growth cycle. Thegrowth cycle is repeated until the film has the desired thickness.

[0033] A multicomponent film is achieved by changing the sourcematerial, i.e. by growing some other oxide onto the growth substratebetween silicon dioxide growth cycles. From the point of view of theinvention the growth order of the oxide compounds can be optional.

[0034] A multicomponent oxide, usually MsiO_(x), is grown by vaporisingthe metal source material and leading the vaporised metal sourcematerial onto the substrate on which it reacts forming one molecularlayer on the surface via a ligand exchange reaction and/or dissociationreaction. After the reaction the reaction space is purged carefully withan inert gas to remove the unreacted source material and the reactionproducts from the reaction space. After this the oxygen source materialis led into the reaction space, said oxygen source material reactingwith the remaining ligands (e.g. chloride ligands) of the chemisorbedmetal compound complex (e.g. zirkonium complex) forming new OH groupsand oxygen bridges on the surface. After the reaction the reaction spaceis purged again carefully. In the next step the above-described growingcycle of silicon dioxide can be carried out.

[0035] In the case of a multicomponent oxide any of the above mentionedsilicon source materials can be used as the silicon compound. It must,however, be noted that also the halide compounds of silicon (silicontetrachloride, silicon tetrafluoride, silicon tetraiodide etc.) as wellas the above mentioned amino compounds are, however, suitable for beingused as silicon source materials. Any of the below specified oxygensources can be used as the oxygen source, most preferably, however,water or ozone.

[0036] One or wore metals or semimetals can function as the secondcation of the multicomponent oxide (i.e. tertiary oxide). Metalsbelonging to the groups IIIa, IVa and Va (transition metals) of theperiodic table of the elements including the rare earth metals, i.e.,lanthane and lanthanoids, as well as the metals and semimetals of groupIVb can especially be mentioned of the metals.

[0037] As the source material for the metal or semimetal (e.g.germanium) any stable vaporisable compound of metal in question can beused. In the example case (see example 2) the following metal sourcematerials were used: aluminium chloride as aluminium source material,titanium tetrachloride (TiCL₄), as titanium source material, tantalumpentachloride (TaCl₅) as tantalum source material, hafnium tetrachloride(HfCL₄) as hafnium source material, zirkonium tetrachloride (ZRCL₄) aszirkonium source material, yttrium betadiketonate (Y(thd)₃) as yttriumsource material and lanthanum betadiketonate (La(thd)₃) as lanthanumsource material. In the example cases water steam (H₂0) was used as theoxygen source with aluminium, titanium, zirkonium and hafnium andtantalum source material and ozone (O₃) was used as the oxygen sourcewith lanthanum and yttrium source material.

[0038] Multicomponent films containing various concentrations of silicondioxide, e.g. SiAlO_(x), SiTiO_(x,) SiTaO_(x,) SiHrO_(x,) SiZrO_(x,)SiYO_(x), SiLaO_(x) can be grown according to the invention by changingthe number of reaction cycles of the silicon source material and ozone.In the formulae above the amount of oxide can vary and the oxide is notalways completely stoichiometric.

[0039] The ratio of the amount of the metal oxide and silicon dioxidecycles can be varied. The number of cycles of the metal oxide can varybetween 1 - 1000 and that of silicon dioxide between 1 - 1000.Preferably the number of cycles of the metal oxide varies between 1 - 50and that of silicon dioxide between 1 - 50. By varying the metal oxidecycle/ silicon dioxide cycle ratio in question e.g. between 10:1 ....1:10 the nature of the mixed oxide can be varied in a controlled wayfrom a complete mixed oxide to a nanolanminate structure.

[0040] In growing of multicomponent oxides it has been found that thegrowth rate of the multicomponent oxide is higher than that of eitherindividual oxide from which the multicomponent oxide is formed. Forexample the growth rate of La₂O₃ from La(thd)₃ and ozone as well as thegrowth rate of Y₂0₃ from Y(thd)₃ and ozone is 0,2 Å/cycle which is atthe same time equal to the growth rate of SiO₂ from 3-aminopropylmethoxysilane and ozone. By preparing the mixed oxide of these metal oxidesmentioned above with silicon dioxide using the cycle ratio of 1:1 agrowth rate of more than threefold, 0,7 Å/cycle, is achieved.

[0041] Any oxygen compound suitable for using in the ALD technology canfunction as the oxygen source in the above silicon dioxide andmulticomponent oxide processes. Preferred oxygen source materials arefor example water, oxygen and hydrogen peroxide and the aqueoussolutions of hydrogen peroxide. Most preferably such oxygen sources areused which are more reactive than water towards silicon compound whichcontains an organic ligand. As mentioned above an especially preferredoxygen source material is ozone (O₃). Ozone can be produced by an ozonegenerator and it is most preferably introduced into the reaction spacewith the aid of nitrogen gas (or inert gas of same kind) whereby theconcentration of ozone is about 1 - 30 vol.-%, preferably about 2 - 25vol.-%.

[0042] By using ozone as the source material organic ligands of siliconsource material, said ligands forming a linear Si-C bond, can be changedat such a temperature in which the other possible ligands of the siliconsource material, for example alkoxy ligands, which form a Si-O-C bondare not uncontrolled decomposing.

[0043] One or more of the following compounds can also be used as theoxygen source material: oxides of nitrogen, such as N_(2O, NO and NO)_(2,) oxyhalide compounds, for example chlorodioxide (ClO_(2) and) perchloroacid (HClO_(4),) peracids (–O–O–H), for example perbenzoicacid (C_(6H) _(5COOOH),)  and peracetic acid (CH_(3COOOH),) alcohols,such as methanol (CH_(3Oh) and ethanol (CH) _(3CH) _(2OH), and) variousradicals, for example oxygen radical (O) or hydroxyl radical (OH).

[0044] The following non-limiting examples illustrate the invention:

Example 1

[0045] SiO₂ films were grown in a flow type F-120 ALCVD™reactor (ASMMicrochemistry Ltd.). 3-aminopropyltriethoxy silaneNH₂-CH₂CH₂CH₂-Si(O-CH₂CH₃)₃ (AMTES), 3-aminopropyltrimethoxy silane(NH₂-CH₂CH₂CH₂-Si(O-CH₃)₃ (AMTMS) and hexamethyldisilazane(CH₃)₃Si-NH-Si(CH₃)₃ (HMDS) were used as the silicon source material.Ozone (0₃) was used as the oxygen source material. AMTES and AMTMS wereinside of the reactor. Ozone and HMDS were led into the reactor fromoutside. The reaction temperature of AMTES was 200 or 300 °C, that ofAMTMS 300 °C and HMDS 400 °C.

[0046] The growing of SiO₂ from AMTES was carried out with the aid ofalternating AMTES and ozone pulses between of which the reaction spacewas purged carefully so that the source materials would not besimultaneously present in the reaction space. The duration of the AMTESpulse was 1,0 s and that of the purging pulse 2,0 s. The duration of theozone pulse was 4,0 s and the duration of the purging pulse 4,0 s. Thegrowth rate of SiO₂ was 0,15 Å/reaction cycle at the reactiontemperature of 300 °C and 0,28 Å/cycle at the reaction temperature of200°C. The refractive index of silicon dioxide grown at 300 °C was 1,4.Using AMTMS as the source material the pulsing times were 0,5 s, 0,5 s,2,0 s and 1,0 s, respectively, and the growth rate was 0,16 Å/reactioncycle.

[0047] The growing of SiO₂ from HMDS was carried out in the same way asabove. The duration of the HMDS pulse was 0,5 s and that of the purgingpulse 2 s. The duration of the ozone pulse was 2,5 s and that of thepurging pulse 1 s. The growth rate was 0,17 Åand the value of therefractive index varied between 1,48 - 1,57.

[0048] Based on the results, ozone can be used together with thevaporisable silicon source material for growing silicon dioxide by theALD process. Of the silicon source materials the advantage of AMTES andAMTMS is the low reaction temperature when ozone is used as the oxygensource. This enables further the preparing of multicomponent oxidessince other than metal chlorides do not stand reaction temperaturesabove 350 °C without decomposing.

Example 2

[0049] Multicomponent oxides were grown in the above reactor using AMTMSas the silicon source material. In the growing processes the AMTMS pulsewas 0,5 s, the purging pulse 0,5 s, the ozone pulse 3,5 s and thepurging pulse 1 s. The pulse of the metal source material wascorrespondingly 0,5 s and the purging pulse 0,5 s. If water was used asthe oxygen source the duration of the water pulse was 0,2 s and that ofthe purging pulse 0,5 s. Using ozone with the metal source material theduration of the ozone pulse was 3,5 s and that of the purging pulse 0,5The growth rates and cycle ratios, are shown in the table below.Multicomponent Metal Source Total Amount of Growth rate Oxide MaterialCycles/Cycle ratio (M:S) Å/cycle SiTiOx TiCl₄ 1800/(1:1) 0,9 SiTaOxTaCl₅ 1800/(1:1) 1,1 SiHfOx HfCl₄  700/(1:1) 1,23 SiZrOx ZrCl₄ 700/(1:1) 1,1 SiZrOx (repeat) ZrCl₄  700/(1:1) 1,1 SiAlOx Al(CH₃₎1900/(1:1) 1,0 SiLaOx La(thd)₃ 1100/(1:1) 0,75 SiYOx Y(thd)₃ 1100/(1:1)0,73 SiYOx Y(thd)₃ 2200/(2:2) 0,74 SiYOx Y(thd)₃ 2200/(5:5) 0,72 SiYOxY(thd)₃ 2200/(10:10) 0,70 SiYOx Y(thd)₃ 2200/(20:20) 0,64 SiYOx Y(thd)₃2240/(40:40) 0,20

[0050] The multicomponent samples were analyzed by ESCA (electronspectroscopy for chemical analysis). The thin film samples were analyzedin three different sites showing that the multicomponent oxides werevery homogenous. Furthermore, the multicomponent oxides were veryuniform which is typical for the ALD process when the chemistry of thegrowing is favourable.

Claims
 1. 30. (New) An atomic layer deposition (ALD) process forproducing a thin film comprising silicon dioxide on a substratecomprising: contacting a substrate with a vaporized silicon compoundsuch that the silicon compound bonds to the substrate, said siliconcompound comprising at least one organic ligand; and converting thebonded silicon compound into silicon dioxide by contacting it with areactive vaporized oxygen source compound.
 2. 31. (New) The process ofClaim 30, wherein the silicon compound is selected from the groupconsisting of silane, siloxane and silazane.
 3. 32. (New) The process ofClaim 30, wherein the boiling point of the silicon compound is less thanor equal to 400°C at a pressure of 10 mbar.
 4. 33. (New) The process ofClaim 30, wherein the silicon compound is selected from the groupconsisting of silicon compounds of the formulas:Si_(m)L_(2m + 2)  wherein  m  is  an  integer  1-3;  

Si_(y)O_(y − 1)L_(2y + 2)  wherein  y  is  an  integer  2-4;  and

Si_(y)NH_(y − 1)L_(2y + 2)  wherein  y  is  an  integer  2-4;

wherein in formulas (I)-(III) each L can independently be F, Cl, Br, I,alkyl, aryl, alkoxy, vinyl (-CH=CH₂), cyano (-CN), amino, silyl (H₃Si-),alkylsilyl, alkoxysilyl, silylene or alkysiloxane, wherein the alkyl andalkoxy groups can be linear or branched and contain at least onesubstituent, with the proviso that at least one L is an organic ligand.5.
 34. (New) The process of Claim 30, wherein the silicon compoundcomprises both an alkyl and an alkoxy group, at least one of which maybe substituted.
 6. 35. (New) The process of Claim 34, wherein thesilicon compound is selected from the group consisting of3-aminoalkyltrialkoxy silane and hexa-alkyldisilazane, wherein the alkyland alkoxy groups comprise from 1 to 10 carbon atoms.
 7. 36. (New) Theprocess of Claim 30, wherein the substrate comprises hydroxyl groups onthe surface thereof that are reactive with the silicon compound.
 8. 37.(New) The process of Claim 30, wherein the substrate comprises oxidegroups on the surface thereof that are reactive with the siliconcompound.
 9. 38. (New) The process of Claim 36, wherein a second siliconcompound that is capable of reacting with the hydroxyl groups is formedin situ.
 10. 39. (New) The process of Claim 38, wherein the secondsilicon compound is a silane.
 11. 40. (New) The process of Claim 39,wherein the formula of the silane is SiL₁L₂L₃L₄, wherein L₁ representsan amino group and L₂₄ represent alkyl or alkoxy groups.
 12. 41. (New)The process of Claim 38, wherein the second silicon compound is formedby contacting the substrate with hexa-alkyldisilazane at 350°C at apressure of 0.1mbar.
 13. 42. (New) The process of Claim 30, wherein thereactive oxygen source compound is selected from the group consisting ofwater, oxygen, hydrogen peroxide, an aqueous solution of hydrogenperoxide, ozone and a mixture thereof.
 14. 43. (New) The process ofClaim 30, wherein the reactive oxygen source compound is a nitrogenoxide.
 15. 44. (New) The process of Claim 43, wherein the reactiveoxygen source compound is selected from the group consisting of N₂O, NOand NO₂.
 16. 45. (New) The process of Claim 30, wherein the reactiveoxygen source compound is selected from the group consisting ofoxyhalides, peracids (-O-O-H), alcohols, oxygen radicals (O^(..)) andhydroxyl radicals (^(.)OH).
 17. 46. (New) The process of Claim 45,wherein the oxyhalide is selected from the group consisting of chlorinedioxide (ClO₂) and perchloro acid (HClO₄).
 18. 47. (New) The process ofClaim 45, wherein the peracid is selected from the group consisting ofperbenzoic acid (C₆H₅COOOH) and peracetic acid (CH₃COOOH).
 19. 48. (New)The process of Claim 45, wherein the alcohol is selected from the groupconsisting of methanol (CH₃OH) and ethanol (CH₃CH₂OH).
 20. 49. (New) Theprocess of Claim 30, wherein the bonded silicon compound is convertedinto silicon dioxide by contacting it with ozone-containing gas having aozone concentration of 1vol.%.
 21. 50. (New) The process of Claim 30,wherein contacting the substrate with a vaporized silicon compound andconverting the bonded silicon compound into silicon dioxide are bothperformed at essentially the same temperature.
 22. 51. (New) The processof Claim 30, wherein the thin film consists essentially of silicondioxide.
 23. 52. (New) The process of Claim 30, wherein the thin film isa multicomponent oxide thin film comprising silicon dioxide and one ormore additional oxides.
 24. 53. (New) The process of Claim 52, whereinthe additional oxide is selected from the group consisting of zirconiumoxide, titanium oxide, hafnium oxide, tantalum oxide, aluminum oxide,yttrium oxide and lanthanum oxide.
 25. 54. (New) The process of Claim53, wherein the additional oxide is produced by contacting the substratewith a halide compound selected from the group consisting of vaporizedhalide compounds of zirconium, aluminum, titanium, hafnium, andtantalum, such that the halidecompound bonds to the substrate andconverting the bonded halide compound into an oxide by contacting itwith a vaporized reactive oxygen source compound.
 26. 55. (New) Theprocess of Claim 54, wherein the reactive oxygen source compoundcomprises water.
 27. 56. (New) An ALD process for producing amulticomponent oxide thin film comprising silicon dioxide on asubstrate, comprising: contacting a substrate with a vaporized siliconcompound such that the silicon compound bonds to the substrate;converting the bonded silicon compound to silicon dioxide; contactingthe substrate with a vaporized metal or semimetal compound other thansilicon such that the metal or semimetal compound bonds to thesubstrate, and converting the bonded metal or semimetal compound to anoxide.
 28. 57. (New) The process of Claim 56, wherein the substrate isalternately contacted with the silicon compound and the other metal orsemimetal compound.
 29. 58. (New) The process of Claim 56, wherein thesilicon compound is converted to silicon dioxide by contacting thebonded silicon compound with a reactive oxygen source compound.
 30. 59.(New) The process of Claim 56, wherein the silicon compound comprises atleast one organic ligand.
 31. 60. (New) The process of Claim 56, whereinthe boiling point of the silicon compound is less than or equal to 400°Cat a pressure of 10 mbar.
 32. 61. (New) The process of Claim 56, whereinthe silicon compound is selected from the group consisting of a halidecompound of silicon and an amino compound of silicon .
 33. 62. (New) Theprocess of Claim 56, wherein the silicon compound is selected from thegroup consisting of silane, siloxane and silazane.
 34. 63. (New) Theprocess of Claim 56, wherein the silicon compound is selected from thegroup consisting of silicon compounds of the formulas:Si_(m)L_(2m + 2)  wherein  m  is  an  integer  1-3;  

Si_(y)O_(y − 1)L_(2y + 2)  wherein  y  is  an  integer  2-4;  and

Si_(y)NH_(y − 1)L_(2y + 2)  wherein  y  is  an  integer  2-4;

wherein in formulas (I)(III) each L can independently be F, Cl, Br, I.Alkyl, aryl, alkoxy, vinyl (₂), cyano (-CN), amino, silyl (H₃Si-),alkylsilyl, alkoxysilyl, silylene or alkylsiloxane, and wherein thealkyl and alkoxy groups can be linear or branched and contain at leastone substituent.
 35. 64. (New) The process of Claim 56, wherein the thinfilm comprises one or more oxides selected from the group consisting ofzirconium oxide, titanium oxide, hafnium oxide, tantalum oxide, aluminumoxide, yttrium oxide and lanthanum oxide.
 36. 65. (New) The process ofClaim 56, wherein the metal or semimetal compound other than silicon isselected from the group consisting of a vaporisable halide compound ofzirconium, aluminum, titanium, hafnium, and tantalum.